Substantive azo dyestuffs



No llbrawi'ng.A Application led February218,'1828;"Seral-Noir25?,789,and'in Germany March` 10, 1927. V,

Patented Mar. 29, 1932 UmTEn-[sTATEs- PATENT .OFFICE RIGHAED s'rssEn, 0FooLoGflvE-DEUirz,Y GERMANY, AssIGNoE To GENERAL yANILINE woEKsrNc.;oEnEw YORK, N. Y., a

A conPonA'rroN or DELAWARE sUBsTANfrrvE Azzol DYEs'rUFEs A The presentiinventi dyestuis.

I have n concerns new Adisazo found that'byl coupling tetrazotized tonicacid, whichmay be otherwise substituted by hydroxyl, new dyestuffs areobtainable which in the free form probably have the general :formulaSOaH benzene series, each of which contain groups causing solubilityuilnwater atleast one of t the couplingl components being a N-phenylnaphthylamine sulfonic acid, which may be otherwise substituted byhydroxyl. The new dyestut'fs are in the form of theirV alkali metalsalts darkpowders which dissolve in strong sulfuric acid with red toblack colorations. They exhibit agood solubility Yin water, especiallyin calcareousv water and dye cotton and regenerated cellulose redtogreen shades which become fast to water, washing and light, .whenatertreat-ed with suitable metal salts 'such as copper?, cobaltchromiumfsaltsand the like. On treatment withlstgm;

pled with 630 parts byvweight of S-hydroiiy-vyl#phenylamino-naphthalene-Lsulfonic acid inl av solutionv renderedalkaline with sodium carbonate and in the .presence'of pyridine Thecoupling mixture is finally heated lto about 400 C., and the dysestufhaving inthe Y tree state the following formula:

' cllooH is salted out and dried. It appears as a black powder, whichdyes cotton blue shades. By

aftertreatn1ent with copper salts the dyeings become morev greenish andat the `same time fastto washing and light. 4 Y l 1 Example 272 parts byweight of 4,4",-

diamino dipheny1-3 3dicarboxylic acid are Y tetrazotized and coupledwith 315 parts by weight of 5-hydroXy2phenyl-naphthy1am+ ine-7-sulfonicacid in alkaline bicarbonate solution. tered and coupledy with 224 partsby weight of 1-hydroXy-naphthalene-5-su1f0nic acid in The intermediateproduct is lil-1 a solution rendered alkaliney with sodium cari stuffhaving'in the free state the'following formula Goan ,l oozH n.

OIL-'1 I is salted out, filtered and dried. It appears as a blackpowder, Which dissolves in Water with a bluish red coloration andV dyescotton and regenerated cellulose reddish violet shades. Byafter-treatment 01E the dyeing With copper salts a blue violet isobtained, fast to Washing and light. On treatment With stannous chlorideand hydrochloric acid, the .dyestuf yields l.l.diamino.diphenylBLW-dicarboxylic acid, 1-hydroXy-2-.a1nino naphthalene-'-sulfonic acidand l-hydroxy- Q-amino-G-phenyl amino-naphthalene-sulfonic acid.

`Ecmzplc 3.-272 parts byl Weight-@4145 diamine diphenyl-S:3-dicarboxylic acid are tetrazotized and lcoupled with 31:5 parfts byWeight of S-.hydroXy-'l-phenyl .ainino-.naphthalene-l-suflfonic fac'idin .alkaline `bicarbonate solution. When the torina-tion oftheintermediate product is complete,.a-solution of 28?? zparts weightosulfo-aceto acetic acidortho.,anis1dide is added. The .mixture isrendered alkaline with sodium 4carbonate and heated tol about 40 C.until coupling is coinplete; the dyestuf is salted out, iltered anddried. It fornis a black powder which dissolves readily in Water with agreyish blue coloration. In its free state it has'the following`:formula lose red to green shades, which become fast to Water, Washingand light by after-treatment With suitable metal salts, yielding whenreated with stannous chloride and hydrochloric acid among other products4.4 -diamine-diphenyl-3adicarboxylic acid.

2. Disazo dyestuis having in their free form the general formula whereinR represents the residue of .a lN- phenyl-naphthylainine-sulfonic acid,which may be substituted by hydroxyl, Rfstands for the residue of anyother coupling component of the 'benzene -or :naphthaleneV seriescontaining a sulf'onic or carboxylic acid g=1'oup,fsaid dyestuffs 4being:in the form of their alkali metal salts .dark-powders, easily solublein Water 4and strong :sulfuric acid .Wiith red to black colorations,dyeing cot-ton and :regenerated cellulose red lto green shades. vwhichbecome fast to Water, 'Washing vand 'light by after-treatment Withsuitable metal salts, yielding `when treated 4with :sta-nilous `chlorideand hydrochloric acid among other products4.4dianiinodiphenyl3.3=dicarboxylic acid.

. SOsH Ondyeingcotton a :greyish blue shade is .obtai-ned, which onafteretreatrnent kWith copper salts, changes to `vav clear vgreen fastto Washing and light.

claim l. 'D'isazo -dyestuffs 'having in their free form the general`formula 3.. vDisazo dyestuli's having 'in their free form the generalformula wherein R :stands for the residue of the cou pling component R1stands for a residue of .any other coupling component of. the benzene ornaphthalene series containing a sulfonic or carboxylic acid group, saiddyestul's being in the form of their `alkali metal salts dark powders,easily solubl'ein Water and strong sulfuric acid with red to blackcolorations, dyeing cotton and regenerated cellulose red to greenshades, Which become fast to Water, Washing and light byafter-,treatment With suitable metal salts, yielding when treateddwithstannous chloride and hydrochloric acid among others4.4!-diamino-diphenyl-32V-dicarboxylic acid and naphthalene-S-sulfonicacid f 4. The disazo dyestu' having in its free form'the probableformula Y f soaH 'I H v n said dyestuj being in the form of its'alkalimetalv salts a black` powder, dissolving in Water and strong sulfuricacid With a bluishred coloration, dyeing cotton and regeneratedcellulose reddish violet shades Which change to a blue-violet fast toWashing andy light by after-treatment with copper salts, yielding ontreatment with stannous chloride andV hydicarboxylic acid,'l-hydroxy-2-amino5-sule fonic acid and 1-hydroXy-2-alnino--phenylvamino-naphthalene--sulfonic'acid.

In testimony whereof I have hereunto set my hand.'

RICHARD STUSSER.

l -hydroXy-Q- amino 6 -phenylamino- Q

